JP4800927B2 - Method for producing lactone or epoxide - Google Patents

Abstract

The present invention relates to a process for the oxidation, in an inert solvent, of a non-aromatic or non-enonic ethylenic bond or of a non-conjugated cyclic ketones into the corresponding epoxides, respectively lactone, using H2O2 as oxidant, a content in water of the reaction medium below 15% w/w and, as sole catalyst, an alkaline or alkaline earth salt or complex.

Description

The present invention relates to the field of organic synthesis. More particularly, the present invention uses H ₂ O ₂ as the oxidizing agent, the water content of the reaction medium is less than 15% w / w, and the only catalyst is an alkali metal or alkaline earth metal salt or complex or said salt or A new method is provided for the oxidation of a substrate having a non-aromatic or non-enone ethylene bond or a non-conjugated cyclic ketone to the corresponding epoxide, lactone, respectively, using a mixture of complexes.

So-called buyer billiger oxidation or olefin epoxidation is one of the reactions well discussed in the state of the art. Of the different main oxidants used in these two types of reactions, H ₂ O ₂ is most noted. However, when using H ₂ O ₂ , it is necessary to add a catalyst capable of generating active species.

Catalysts used in processes reported in the state of the art using H ₂ O ₂ as oxidant are heavy metal derivatives, such as salts, complexes, silicates or oxides or percarboxylic acid derivatives or precursors of said acid derivatives, such as nitriles , Carboxylic acid or carboxylic anhydride or a mixture of chloride and H ₂ O ₂ . Here, the heavy metal means a metal different from an alkali metal or an alkaline earth metal.

Examples of these known methods include S. Ueno et al., Chem. Commun. Reference can be made to the process described in 1998, 295, where the olefin is epoxidized in the presence of H ₂ O ₂ , hydrotalcite (Mg ₁₀ Al ₁₂ (OH) ₂₄ CO ₃ ) and benzonitrile. Or optionally A. M.M. d'A. Rocha Gonzalves et al. Chem. Research, 1991, 208 can be cited, where a buffered solution of a percarboxylic acid derivative is used to epoxidize the olefin. Newer is M.M. C. A. van "Vliet et al., Green Chemistry 2001, 243 describe an epoxidation process using alumina as a catalyst.

  The disadvantages of these state-of-the-art methods are that they are often toxic at the end of the reaction and require extensive processing work to remove the catalyst as a contaminant. The end result of this treatment is the formation of significant amounts of waste that can potentially threaten the environment. Furthermore, the treatment can lead to the degradation of large amounts of the desired lactone or epoxide at the beginning, resulting in a loss of efficiency in the whole process.

  Accordingly, there is a need to develop an industrial process for carrying out environmentally friendly, for example, so-called green chemistry type buyer billiard reactions and olefin epoxidation.

In order to solve the above problems, the present invention consists of mild conditions,
Provided is a new process aimed at oxidizing a substrate containing i) a non-aromatic or non-enone ethylene bond or ii) a non-conjugated cyclic ketone to the corresponding epoxide or lactone, said process being carried out in an inert solvent The process is carried out in the presence of a catalyst system using H ₂ O ₂ as oxidant, wherein the process has a water content of the reaction medium of less than 15% w / w and the catalyst system is an alkali metal or alkaline earth metal salt Or it consists of a compound selected from the group which consists of a complex and the said salt or the mixture of a complex, It is characterized by the above-mentioned.

  The process according to the invention thus has the advantage that the addition of percarboxylic acid derivatives or precursors or heavy metal derivatives to the reaction medium is avoided, for example as a co-reactant or co-catalyst.

  Percarboxylic acid derivatives have the formula:

の官能基を有する任意の化合物を意味し、
式中、Ｒは水素原子または炭素原子または酸素原子を有する任意の基を表す。更に重金属誘導体はアルカリ金属またはアルカリ土類金属でない金属を含有する任意の化合物を意味し、例えば遷移金属、アルミニウム、ホウ素およびランタニド錯体および酸化物が含まれる。

Means any compound having the functional group
In the formula, R represents a hydrogen atom, a carbon atom, or an arbitrary group having an oxygen atom. Furthermore, heavy metal derivatives mean any compound containing a metal that is not an alkali metal or alkaline earth metal, including, for example, transition metals, aluminum, boron and lanthanide complexes and oxides.

Surprisingly, under suitable test conditions, which means a water content of the reaction medium of less than 15% w / w, the substrate H ₂ O ₂ is otherwise inert to the alkali metal or alkaline earth metal derivative. It has been found that oxidation by can be promoted.

  The term non-aromatic or non-enone ethylene bond means an olefin in which the C═C functional group is not part of an aromatic ring or is not conjugated with a carbon-oxygen double bond.

  Similarly, the term non-conjugated cyclic ketone means a C═O functional group in which the carbon atom is part of a cyclic hydrocarbon unit and is not conjugated with a carbon-carbon double bond or a carbon-heteroatom double bond. When an α, β-unsaturated carbonyl group or enone group is used as a substrate in the method of the present invention, It should be noted that unlike the chemistry first recognized by Weitz, it does not react (see, eg, HO House et al., J. Am. Chem. Soc. 1958, 80, 2428).

  Hereinafter, a substance having a non-aromatic or non-enone ethylene bond or a non-conjugated cyclic ketone is described as a substrate.

  According to a first embodiment of the invention, the substrate is a compound of general formula (I) and a compound of general formula (II):

からなる群から選択され、上記式中、
Ｒ^１基は置換されていてもよい、直鎖状、分枝状または環状Ｃ_１〜Ｃ_２０飽和または不飽和炭化水素基を表し、
Ｒ^２基はそれぞれ水素原子、および置換されていてもよい、直鎖状、分枝状または環状Ｃ_１〜Ｃ_２０飽和または不飽和炭化水素基からなる群の中で選択される基を表し、前記Ｒ^２基の２つまたはＲ^２基とＲ^１基は場合により一緒に結合して、置換されていてもよい、モノシクロ、ビシクロまたはトリシクロ誘導体の形の非芳香族Ｃ_５〜Ｃ_２０飽和または不飽和環を形成し、
指数ｍは１〜１０の整数を表し、
Ｒ^３基はそれぞれ水素原子、および置換されていてもよい、直鎖状、分枝状または環状Ｃ_１〜Ｃ_２０飽和または不飽和炭化水素基からなる群の中で選択される基を表し、前記Ｒ^３基の少なくとも２個は場合により一緒に結合して、置換されていてもよい、モノシクロ、ビシクロまたはトリシクロ誘導体の形のＣ_５〜Ｃ_２０飽和または不飽和環を形成し、
Ｘ基はそれぞれＲ^３Ｃ＝ＣＲ^３またはＣ（Ｒ^３）_２基を表し、
前記Ｒ^１，Ｒ^２、Ｒ^３基および前記基により形成される可能な環は場合によりカルボニル、カルボキシルおよびエーテルからなる群から選択される５個までの官能基を有することができる。

Selected from the group consisting of:
The R ¹ group represents an optionally substituted linear, branched or cyclic C ₁ -C ₂₀ saturated or unsaturated hydrocarbon group;
Each R ² group represents a hydrogen atom and a group selected from the group consisting of optionally substituted linear, branched or cyclic C ₁ -C ₂₀ saturated or unsaturated hydrocarbon groups; joined together optionally two or R ² groups and R ¹ groups of said R ² groups, which may be substituted, monocyclic, non-aromatic form bicyclo or tricyclo derivative C ₅ -C ₂₀ saturated or Forming an unsaturated ring,
The index m represents an integer of 1 to 10,
Each R ³ group represents a hydrogen atom and a group selected from the group consisting of optionally substituted linear, branched or cyclic C ₁ -C ₂₀ saturated or unsaturated hydrocarbon groups; wherein at least two R ³ groups are joined together optionally may be substituted, to form monocyclic, a C ₅ -C ₂₀ saturated or unsaturated ring in the form of bicyclo or tricyclo derivative,
Each X group represents an R ³ C═CR ³ or C (R ³ ) ₂ group;
The R ¹ , R ² , R ³ groups and possible rings formed by said groups can optionally have up to 5 functional groups selected from the group consisting of carbonyl, carboxyl and ether.

Possible substituents of the R ¹ , R ² and R ³ groups and possible rings formed by said groups are C ₁ -C ₆ alkyl or alkenyl groups, OR ⁴ groups, carbonyl groups, ester units of the formula COOR ⁵ ; C≡CR ⁴ acetylene unit, halogen atom, C ₂ epoxide, and nitro group, R ⁴ represents a hydrogen atom or a C ₁ -C ₆ saturated or unsaturated group, and R ⁵ is C ₁ -C ₆ saturated or Represents an unsaturated group.

  Saturated or unsaturated hydrocarbon group or ring means a group which is for example aromatic, alkylaromatic, alkyl, alkenyl, alkadienyl or alkatrienyl derivatives.

  When using a substrate of formula (I) or (II) in the process of the invention, the corresponding epoxide or lactone produced is of the formula:

の物質であり、
式中、ｍ、Ｘ、Ｒ^１、Ｒ^２およびＲ^３は式（Ｉ）および（ＩＩ）に記載された意味を表す。

The substance of
In the formula, m, X, R ¹ , R ² and R ³ represent the meanings described in formulas (I) and (II).

According to one particular mode of realizing the first embodiment of the present invention, the method of the present invention is particularly advantageous for the oxidation of substrates of formula (I) or (II), wherein R ¹ group is substituted Represents a linear, branched or cyclic C ₁ -C ₁₀ saturated or unsaturated hydrocarbon group which may be substituted, wherein the R ² groups are each a hydrogen atom and optionally substituted linear, branched, represents branched or cyclic C ₁ -C ₁₀ saturated or group selected in the group consisting of unsaturated hydrocarbon groups, bonded together by case 2 or R ² groups and R ¹ groups of said R ² groups Forming a non-aromatic C ₅ -C ₁₄ saturated or unsaturated ring in the form of an optionally substituted monocyclo, bicyclo or tricyclo derivative,
The index m represents an integer of 1 to 4,
R ³ groups each represent a hydrogen atom and a group selected from the group consisting of an optionally substituted linear, branched or cyclic C ₁ -C ₁₀ saturated or unsaturated hydrocarbon group, At least two of the R ³ groups are optionally joined together to form an optionally substituted C ₅ -C ₁₄ saturated or unsaturated ring in the form of a monocyclo, bicyclo or tricyclo derivative;
Each X group represents an R ³ C≡CR ³ or C (R ³ ) ₂ group;
The R ¹ , R ² and R ³ groups and the possible rings formed by said groups can optionally have up to 5 functional groups selected from the group consisting of carbonyl, carboxyl and ether.

The general definition of the substrate, in the realization form of a functional group may be present in the R ¹ to R ³ radicals is understood that it is not oxidized is conjugated with ethylenic bonds or ketone.

  According to a second embodiment of the invention, the substrate is of the formula

のトリグリセリド油であり、
上記式中、Ｒ^６基はそれぞれ直鎖状、分枝状Ｃ_２〜Ｃ_２０アルケニル、アルカジエニル、またはアルカトリエニル基を表す。有利にＲ^６基はそれぞれ直鎖状または分枝状Ｃ_１４〜Ｃ_２０アルケニル、アルカジエニルまたはアルカトリエニル基を表す。

Triglyceride oil,
In the above formula, each R ⁶ group represents a linear or branched C ₂ -C ₂₀ alkenyl, alkadienyl, or alkatrienyl group. Preferably the R ⁶ groups each represent a linear or branched C ₁₄ -C ₂₀ alkenyl, alkadienyl or alkatrienyl group.

According to another mode of realization of embodiments of the present invention, useful substrates may yield epoxides or lactones that are effective intermediate products or end products in the fields of flavors, flavorings, food, agrochemicals, pharmaceuticals or polymer industries. It is a possible substance. Non-limiting examples of materials that can be used in the embodiments include α- and β-pinene, isoamylene, butadiene polymers, styrene, unsaturated vegetable or animal oils such as soybean oil, sunflower oil, linseed oil, or rapeseed oil, C _6- Cyclopentanone or cyclohexanone optionally substituted by a _C18 linear or branched mono-substituted olefin, one or two linear or branched C ₁ -C ₉ alkyl or alkenyl groups, of octahydronaphthalene C ₁₁ -C ₁₆ bicyclo or tricyclo derivative, such as 9-ethylidene-4-methyl-tricyclo [6.2.1.0 (2,7)] undec-4-ene, 4-methyl-tricyclo [6.2. 1.0 (2,7)] undec-4-ene or 4,7,11,11-tetramethyltricyclo [5.4. .0 (1,3)] undec-4-ene and their optically active isomers, and _C 6 _{-C 16} mono-, bi- or tri-cycloalkene derivatives such cyclooctene, cyclododecene, cyclododecatriene, trimethyl cyclododecatriene And a compound selected from the group consisting of 4,11,11-trimethyl-8-methylenetricyclo [7.2.0] undec-4-ene, cedrene and optically active isomers thereof.

As mentioned above, the process of the present invention is carried out in the presence of an inert solvent. The term inert solvent means a solvent that is not oxidized by H ₂ O ₂ and does not react with the compound of formula (I) or (II) under the reaction conditions.

Any solvent that is generally inert under the test conditions and can solubilize the substrate and H ₂ O ₂ is particularly appreciated. In one specific embodiment of the invention, the solvent is preferably a group consisting of aromatic compounds, ethers, esters, acyclic ketones, alcohols, glycols, amides, phosphates, halogenated hydrocarbons, and mixtures of said solvents. Selected from. Examples of these solvents are halogenated benzene or _toluene, C 4 _{-C 10 ethers,} C 4 -C _{8 ester,} C 4 -C ₇ non-cyclic _ketones, C 1 -C ₆ primary, secondary or tertiary Primary alcohols, ethylene glycol or propylene glycol, and ethylene oxide or propylene oxide oligomers, C _{4 to} C ₆ amides, C _{6 to} C ₂₄ phosphates, methane derivatives having at least two halogen atoms. Particularly suitable solvents are chlorobenzene, t-amyl alcohol, t-butyl methyl ether, t-amyl methyl ether, dioxane, ethyl acetate, ethyl propionate, n-propyl acetate, n-propyl acetate, n-propyl formate, Butyl formate, isopropyl acetate, butyl acetate, and isobutyl acetate can be described.

  In addition, the inert solvent is preferably used in its anhydrous form, for example in a form containing less than 5% water, preferably less than 1% water, based on the weight of the solvent.

  The amount of solvent used in the process of the invention is practically important, provided that it is sufficient to dilute the reactants, for example to allow effective removal or dilution of water present in the reaction medium. Not. For example, as a non-limiting example, an amount in the range of 10-80%, preferably 30-70% of the reaction medium can be described.

Another essential element of the process of the present invention is a catalyst system. The term catalyst system means the entire set of compounds that are added to the reaction medium to achieve activation of H ₂ O ₂ and thus oxidation of the substrate.

Examples of compounds that can form a catalyst system are selected from the following group.
A) Formula MX, M′X ₂ , R ⁷ COOM, (R ⁷ COO) ₂ M ′, M ₂ CO ₃ , MHCO ₃ , M′CO ₃ , MOOH, M ₂ O ₂ , M′O ₂ , MOR ⁷ , And M ′ (OR ⁷ ) ₂ , M represents an alkali metal, M ′ represents an alkaline earth metal, X represents a halogen atom, and R ⁷ may be a hydrogen atom or a halogenated represents a linear, branched or cyclic _C 1 _{-C 15} alkyl or aromatic group,
B) a polycarboxylate M or M ', polycarboxylates carboxyl group portions are fully deprotonated, such as sodium polyacrylate,
_C) C 5 ~C ₂₀ β- dialdimine, beta-diketimine, beta-diketone or beta-ketoester and _C 5 _{-C 20} crown ether, cryptand, alkali having a ligand selected from the group consisting of po da command or Schiff base Metal salts or alkaline earth metal salts or complexes and mixtures of the compounds described in D) A), B) and C).

The process of the present invention, in which the catalyst system is selected from the following group, has proved particularly noteworthy and advantageous.
E) Formulas R ⁸ COOM, (R ⁸ COO) ₂ M ′, M ₂ CO ₃ , MHCO ₃ , M′CO ₃ , M ₂ O ₂ , M′O ₂ , MOR ⁸ , and M ′ (OR ⁸ ) ₂ Wherein M represents Li, Na or K, M ′ represents Mg or Ca, R ⁸ represents a hydrogen atom or a linear, branched or cyclic C ₁ -C ₈ alkyl group,
F) type alkali metal salt or complex of ML, it is wherein L is a _C 5 _{-C 15} diketonate or deprotonated β- ketoester,
G) Mixtures of the compounds described in E) and F).

Examples of R ⁸ COO—, OR ⁸ —, β-diketonate and deprotonated β-ketoester are acetate, propionate, 2-ethylhexanoate, naphthenate, benzoate, 2,4-dichlorobenzoate, propyrate, ethylate, t- _{pentylate, [(CH 3) 3 CCOCHCOC} (CH 3) 3] -, [F 3 CCOCHCOCF 3] -, [C 6 H 5 COCHCOCH 3] -, [CH 3 COCHCOCH 3] - and [CH3COCHCOOCH ₂ CH ₂ OCH _3] ^- it is.

According to one more specific embodiment of the invention, the aforementioned Li, Na or K salts or complexes, in particular Li or Na, produce particularly remarkable results. Similarly, according to one more specific embodiment of the present invention, carbonates, hydrogenocarbonates, acetates, propylates or the aforementioned C ₅ -C ₁₅ β-diketonate salts are particularly useful.

The amount of catalyst added to the reaction mixture may vary over a fairly wide range of values. For example, as a non-limiting example, a molar ratio of catalyst per substrate in the range of 10 ^{−5 to} 0.9, more preferably 0.001 to 0.2 or 0.005 to 0.1 can be described.

The oxidizing agent of the present invention is H ₂ O ₂ . For the purposes of the present invention, an aqueous solution of H ₂ O ₂ can be used, for example a 50-70% by weight aqueous solution of hydrogen peroxide. However, as can be appreciated from what has already been described and described below, according to one specific embodiment of the invention it is more advantageous to use a solution of H ₂ O ₂ in an organic solvent, This contributes to keeping the water content of the reaction medium as low as possible. Of particular interest are aqueous solutions of H ₂ O ₂ in organic solvents such as C ₄ -C ₆ esters or ethers, tertiamyl alcohol or chlorobenzene. The expression water-free means a solution containing less than 5%, preferably less than 1% water. The solution can be obtained by the method described in EP98427.

Useful amounts of H ₂ O ₂ added to the reaction mixture can be formed in a fairly wide range of values. For example, as a non-limiting example, the molar ratio of H ₂ O ₂ per functional group to be oxidized in the substrate of formula (II) in the range 0.5-2, more preferably in the range 0.9-1.2. Can be described.

  Another feature of the process of the present invention is the presence of less than 15% w / w water in the reaction medium. If the amount of water exceeds the above limit, no reaction takes place or a large amount of by-product is formed. In fact, the lower the water content of the reaction medium, the better the reaction. It is therefore advantageous to have a water content in the reaction medium of less than 5% w / w or less than 1% w / w, according to a specific configuration of the invention.

In order to maintain the water content at this low limit, it is possible to use, for example, a highly concentrated aqueous solution of hydrogen peroxide and a sufficient amount of anhydrous solvent or an aqueous solution of H ₂ O ₂ in an organic solvent. In other cases, it is possible to continuously remove the water formed and introduced from the reaction medium during the process. This can be accomplished by any means known to those skilled in the art, such as azeotropic distillation.

  The temperature at which the process of the invention can be carried out consists of a temperature between 5 ° C. and the reflux temperature of the solvent. The temperature is preferably in the range from 60 ° C to 140 ° C. One skilled in the art can of course select advantageous temperatures as a function of the melting and boiling points of the starting and final products and the solvent.

According to the simplest mode of realization of the present invention, the present invention is non-aromatic using an oxidant consisting of an inert organic solvent, a suitable amount of H ₂ O ₂ , a catalyst system and less than 15% w / w water. Alternatively, it comprises a method of oxidizing a substrate having a non-enone ethylene bond or a non-conjugated cyclic ketone to the corresponding epoxide or lactone, respectively, wherein% relates to the total mass of the oxidizing agent.

The oxidizing agent is an object of the present invention. Substrates, catalyst systems, solvents and H ₂ O ₂ are described.

The proportions in which the various components of the oxidizer can be mixed together can vary within the following ranges. a) H ₂ O ₂ 2-20%, preferably 10-15%, b) catalyst 0.001-10%, preferably 0.1-2%, c) water less than 15%, solvent removes the remainder of the mixture % Is related to the total mass of oxidant. The water content of the oxidizing agent is less than 5% or less than 3%.

  The invention is illustrated in more detail by the following examples, in which abbreviations have their usual meaning in the art, and temperatures are expressed in degrees Celsius (° C.).

Example 1
Buyer billiger oxidation of pentylcyclopentanone

Process A)
Into a 250 ml three-necked flask equipped with a magnetic stirrer and a reflux condenser, 31 g (0.2 mol) of 2-pentylcyclopentanone, 31 g of anhydrous ethyl propionate and 0.048 g (1 mol%) of anhydrous lithium hydroxide were introduced. The mixture was refluxed at about 100 ° C. Subsequently, 57.5 g (0.22 mol) of an anhydrous 13% w / w hydrogen peroxide solution in ethyl propionate, obtained by extraction of 70% anhydrous H ₂ O ₂ solution with ethyl propionate, was added over 4 hours. Slowly added to the reactor and maintained at reflux for 2 hours after the end of the introduction. The reaction mixture was subsequently washed with 10% water to remove unreacted H ₂ O ₂ and finally distilled to remove the solvent.
GC analysis of the residue showed 18% unreacted 2-pentylcyclopentanone (82% reaction), 73% lactone and 19% by-product.

Process B)
The reaction was carried out as in step A), but 0.22 mol of H ₂ O _{2 in} the form of a 70% by weight aqueous solution was used.
The conversion rate was 53%, and the selectivity of lactone was 61%.

Process C)
In a 250 ml three-necked flask equipped with a magnetic stirrer and Dean Stark reflux condenser, 61.6 g (0.4 mol) 2-pentylcyclopentanone, 100 g anhydrous ethyl propionate solvent and 0.1 g anhydrous lithium hydroxide (1 mol%) was introduced and the mixture was refluxed at about 110 ° C. Subsequently, 21.5 g (0.44 mol) of a 70% w / w H ₂ O ₂ aqueous solution was added to the reactor over 4 hours, and the initial water and the water formed were 90:10 ethyl propionate / water azeotrope. And ethyl propionate was fed back into the reactor. The reaction mixture was subsequently maintained at reflux for 2 hours, cooled to 30 ° C. and subsequently washed with 10% water to remove unreacted H ₂ O ₂ and finally distilled to recover the solvent. GC analysis of the residue distilled from bulb to bulb showed 0.5% unreacted 2-pentylcyclopentanone (99.5% reaction) and 96% lactone.

Example 2
Buyer Billiger Oxidation of Pentylcyclopentanone Using Various Catalysts This example illustrates the action of the catalyst used in the buyer billigar oxidation of 2-pentylcyclopentanone to lactone with H ₂ O ₂ .
The reaction was carried out in the presence of 1 mol% catalyst in ethyl propionate as solvent at 110 ° C. under the same conditions as described in Example 1, Step C). The results are listed in Table 1.

収率は使用される基質の全量に関して計算した。
反応を例１、工程Ｃ）に記載される条件と同じ条件下で、還流で溶剤としてｔ−アミルアルコール中で、１モル％触媒の存在で実施した場合に、表１ａに記載される同様の結果が得られた。

The yield was calculated with respect to the total amount of substrate used.
When the reaction was carried out under the same conditions as described in Example 1, Step C), in t-amyl alcohol as solvent at reflux, in the presence of 1 mol% catalyst, the same as described in Table 1a Results were obtained.

収率は使用される基質の全量に関して計算した。

The yield was calculated with respect to the total amount of substrate used.

Example 3
Buyer-bilger oxidation of pentylcyclopentanone using various solvents. This example is from 2-pentylcyclopentanone to lactone with a 70% w / w aqueous H ₂ O ₂ solution at 110 ° C. and in the presence of 1 mol% lithium acetate. The action of the solvent used in the buyer's billiard oxidation will be described.
The reaction was carried out under the same conditions as described in Example 1, Step C). The results are listed in Table 2.

収率は使用される基質の全量に関して計算した。

The yield was calculated with respect to the total amount of substrate used.

Example 4
Buyer Billiger Oxidation of Various Non-Conjugated Cyclic Ketones This example demonstrates the oxidation of various ketones with 70% w / w aqueous H ₂ O ₂ solution in ethyl propionate as a solvent at 110 ° C. in the presence of 1 mol% lithium acetate. explain. The reaction was carried out under the same conditions as described in Example 1, Step C). The results are listed in Table 3.

収率は使用される基質の全量に関して計算した。

The yield was calculated with respect to the total amount of substrate used.

Example 5
Epoxidation of 1,5,9-cis, trans, trans-cyclododecatriene (CDT)

磁気撹拌機およびディーンシュターク還流冷却器を有する２５０ｍｌ三首フラスコにＣＤＴ６４．８ｇ（０．４モル）、無水エチルプロピオネート溶剤１００ｇおよび１モル％無水リチウムビス（ピバロイル）メタン［Ｌｉ（ｂｐｍ）］を導入した。混合物を約１１０℃で還流し、７０％ｗ／ｗ水性Ｈ_２Ｏ_２２０ｇ（０．４モル）を反応器に４時間にわたり緩慢に添加した。最初の水および形成された水を９０：１０エチルプロピオネート、水共沸混合物として除去し、エチルプロピオネートを反応器に再び供給した。反応混合物を１１０℃で還流下に保った後に、反応器内容物を冷却し、１０％水で洗浄し、未反応Ｈ_２Ｏ_２を除去し、最後に蒸留し、溶剤を回収した。
残留物のバルブからバルブへの蒸留によりＣＤＴ３１％、エポキシシクロドデカジエン（ＣＤＤＯ）６３％および副生成物６％を生じた。

In a 250 ml three-necked flask equipped with a magnetic stirrer and a Dean-Stark reflux condenser, 64.8 g (0.4 mol) of CDT, 100 g of anhydrous ethyl propionate solvent and 1 mol% anhydrous lithium bis (pivaloyl) methane [Li (bpm)] Was introduced. The mixture was refluxed at about 110 ° C. and 20 g (0.4 mol) of 70% w / w aqueous H ₂ O ₂ was slowly added to the reactor over 4 hours. Initial water and water formed were removed as a 90:10 ethyl propionate, water azeotrope and ethyl propionate was fed back into the reactor. After keeping the reaction mixture under reflux at 110 ° C., the reactor contents were cooled and washed with 10% water to remove unreacted H ₂ O ₂ and finally distilled to recover the solvent.
Distillation of the residue from bulb to bulb yielded 31% CDT, 63% epoxycyclododecadiene (CDDO) and 6% by-product.

Example 6
Epoxidation of CDT using various catalysts This example illustrates the effect of the catalyst used for the epoxidation of CDT with 70% w / w aqueous H ₂ O ₂ in ethyl propionate as a solvent at 110 ° C. The reaction was carried out in the presence of 1 mol% catalyst in the presence of 1 mol% catalyst under the same conditions as described in Example 5. The results are listed in Table 4.

収率は使用される基質の全量に関して計算した。
ｂｐｍ＝ビス（ピバロイル）メタン、ｈｆａｃａｃ＝ヘキサフルオロアセチルアセトン、ＭｅＯＥｔＡｃａｃ＝２−メトキシエチルアセトアセテート、ａｃａｃ＝アセチルアセトン。

The yield was calculated with respect to the total amount of substrate used.
bpm = bis (pivaloyl) methane, hfacac = hexafluoroacetylacetone, MeOEtAcac = 2-methoxyethyl acetoacetate, acac = acetylacetone.

Example 7
Epoxidation of CDT with various solvents. This example epoxidizes CDT with 70% w / w aqueous H ₂ O ₂ at 110 ° C. in the presence of 1 mol% LiOAc under the same conditions as described in Example 5. The action of the solvent used in the above will be described. The results are listed in Table 5.

収率は使用される基質の全量に関して計算した。

The yield was calculated with respect to the total amount of substrate used.

Example 8
Epoxidation of various substrates The following examples illustrate the epoxidation of various alkenes with 70% w / w aqueous H ₂ O _{2 in} ethyl propionate as a solvent at 110 ° C. in the presence of 1 mol% lithium acetate. The reaction was carried out under the same conditions as described in Example 5. The results are listed in Table 6.

収率は使用される基質の全量に関して計算した。

The yield was calculated with respect to the total amount of substrate used.

Claims (23)

An epoxide production method for producing a corresponding epoxide by oxidizing a substrate containing a non-aromatic or non-enone ethylene bond,
In the above-mentioned production method, the presence of the catalyst system using H ₂ O ₂ activated by a catalyst system (excluding heavy metal derivatives and percarboxylic acid derivatives) as an oxidant in a solvent composed of only an inert solvent. Below, the compound of the following general formula (I) selected as the substrate is reacted.

[In the above formula (I),
The R ¹ group represents an optionally substituted linear, branched or cyclic C ₁ -C ₂₀ saturated or unsaturated hydrocarbon group;
Each R ² group represents a hydrogen atom and a group selected from the group consisting of optionally substituted linear, branched or cyclic C ₁ -C ₂₀ saturated or unsaturated hydrocarbon groups; joined together optionally two or R ² groups and R ¹ groups of said R ² groups, which may be substituted, monocyclic, non-aromatic form bicyclo or tricyclo derivative C ₅ -C ₂₀ saturated or Forming an unsaturated ring,
The possible rings formed by the R ¹ , R ² group or the two R ² groups can optionally have up to 5 functional groups selected from the group consisting of carbonyl, carboxyl and ether] ,
As the corresponding epoxide, a compound represented by the following formula (I ′) is obtained,

The water content of the reaction medium is less than 15% w / w,
Said catalyst system comprises the following A) formulas R ⁷ COOM, (R ⁷ COO) ₂ M ′, M ₂ CO ₃ , MHCO ₃ , M′CO ₃ , MOOH, M ₂ O ₂ , M′O ₂ , MOR ⁷ , And M ′ (OR ⁷ ) ₂ , M represents an alkali metal, M ′ represents an alkaline earth metal, and R ⁷ represents a hydrogen atom or a linear, branched or cyclic C ₁ -C ₁₅ alkyl. Or represents an aromatic group which may be halogenated;
B) a polycarboxylate M or M ', polycarboxylates carboxyl group portion is completely deprotonated;
_C) C 5 ~C ₂₀ β- dialdimine, beta-diketimine, beta-diketone or beta-ketoester and _C 5 _{-C 20} crown ether, cryptand, alkali having a ligand selected from the group consisting of po da command or Schiff base metal or alkaline earth metal salt or complex; and D) a), B) and C) Ri Do because only a compound selected from the group consisting of the compounds described in, also,
The inert solvent is a solvent that is not oxidized by H ₂ O ₂ and does not react with the compound of formula (I) under reaction conditions.
An epoxide manufacturing method characterized by the above. The R ¹ group represents an optionally substituted linear, branched or cyclic C ₁ -C ₁₀ saturated or unsaturated hydrocarbon;
R ² groups each represent a hydrogen atom and a group selected from the group consisting of optionally substituted linear, branched or cyclic C ₁ -C ₁₀ saturated or unsaturated hydrocarbon groups, ^{Two of the} R ² groups or the R ² and R ¹ groups are optionally joined together to form a non-aromatic C _{5 to} C ₁₄ saturated or optionally substituted monocyclo, bicyclo or tricyclo derivative. Forming an unsaturated ring,
The possible rings formed by the R ¹ , R ² group or the two R ² groups can optionally have up to 5 functional groups selected from the group consisting of carbonyl, carboxyl and ether. Item 2. The method according to Item 1. An epoxide production method for producing a corresponding epoxide by oxidizing a substrate containing a non-aromatic or non-enone ethylene bond,
In the above-mentioned production method, the presence of the catalyst system using H ₂ O ₂ activated by a catalyst system (excluding heavy metal derivatives and percarboxylic acid derivatives) as an oxidant in a solvent composed of only an inert solvent. The following epoxide is obtained by reacting a triglyceride oil of the following general formula (III) selected as the substrate below:

[Wherein the R ⁶ groups each represent a linear or branched C ₂ -C ₂₀ alkenyl, alkadienyl or alkatrienyl],
The water content of the reaction medium is less than 15% w / w,
Said catalyst system comprises the following A) formulas R ⁷ COOM, (R ⁷ COO) ₂ M ′, M ₂ CO ₃ , MHCO ₃ , M′CO ₃ , MOOH, M ₂ O ₂ , M′O ₂ , MOR ⁷ , And M ′ (OR ⁷ ) ₂ , M represents an alkali metal, M ′ represents an alkaline earth metal, and R ⁷ represents a hydrogen atom or a linear, branched or cyclic C ₁ -C ₁₅ alkyl. Or represents an aromatic group which may be halogenated;
B) a polycarboxylate M or M ', polycarboxylates carboxyl group portion is completely deprotonated;
_C) C 5 ~C ₂₀ β- dialdimine, beta-diketimine, beta-diketone or beta-ketoester and _C 5 _{-C 20} crown ether, cryptand, alkali having a ligand selected from the group consisting of po da command or Schiff base metal or alkaline earth metal salt or complex; and D) a), B) and C) Ri Do because only a compound selected from the group consisting of the compounds described in, also,
The inert solvent is a solvent that is not oxidized by H ₂ O ₂ and does not react with the triglyceride oil of the formula (III) under reaction conditions.
An epoxide manufacturing method characterized by the above. Wherein the substrate is, alpha and β-pinene, isoamylene, butadiene polymers, styrene, unsaturated vegetable or animal oils, C ₆ -C ₁₈ is selected from the group consisting of linear or branched monosubstituted olefins, according to claim 1, wherein Epoxide production method. Before Ki溶 agent, aromatic compounds, ethers, esters, acyclic ketones, alcohols, glycols, amides, phosphates, halogenated hydrocarbons, and is selected from the group consisting of a mixture thereof, according to claim 1 or 3, wherein Epoxide production method. Before Ki溶 agent, chlorobenzene, t-amyl alcohol, t- butyl methyl ether, t-amyl methyl ether, dioxane, ethyl acetate, ethyl propionate, n- propyl acetate, n- propyl formate, butyl formate, The epoxide production method according to claim 5, wherein the epoxide production method is selected from the group consisting of isopropyl acetate, butyl acetate and isobutyl acetate. The catalyst system is the following: E) Formula R ⁸ COOM, (R ⁸ COO) ₂ M ′, M ₂ CO ₃ , MHCO ₃ , M′CO ₃ , M ₂ O ₂ , M′O ₂ , MOR ⁸ , And M ′ (OR ⁸ ) ₂ , M represents Li, Na or K, M ′ represents Mg or Ca, R ⁸ represents a hydrogen atom or a linear, branched or cyclic C _{1 to} C _8. Represents an alkyl group;
F) an alkali metal salt or complex of formula ML, wherein L is a C _{5 to} C ₁₅ β-diketonate or deprotonated β-keto ester; and G) from a mixture of compounds described in E) and F) The epoxide production method according to claim 1 or 3, comprising only a compound selected from the group consisting of: ^{R 8 COO -, - OR 8} , β- diketonate and deprotonated beta-ketoester acetate, propionate, 2-ethylhexanoate, naphthenate, benzoate, 2,4-dichloro benzoate, propylate, ethylate, t-pentylate, _{[(CH 3) 3 CCOCHCOC (} CH 3) 3] -, [F 3 CCOCHCOCF 3] -, [C 6 H 5 COCHCOCH 3] -, [CH 3 COCHCOCH 3] - and _{[CH 3 COCHCOOCH 2 CH 2 OCH} 3 ] ^- it can be, epoxide process according to claim 7 wherein.   The epoxide production method according to claim 1 or 3, wherein the catalyst system is a salt or complex of Li, Na or K. The catalyst system, carbonates, hydrogenoformans carbonate, acetate, propylate, or C ₅ -C ₁₅ beta-diketonate is a salt or complex, according to claim 1 or 3 epoxide manufacturing method described.   The epoxide production method according to claim 1 or 3, wherein the water content of the reaction medium is less than 5% w / w.   The epoxide production method according to claim 1 or 3, wherein water is continuously removed from the reaction medium. A method for producing a lactone by oxidizing a substrate containing a non-conjugated cyclic ketone to produce a corresponding lactone,
In the above-mentioned production method, the presence of the catalyst system using H ₂ O ₂ activated by a catalyst system (excluding heavy metal derivatives and percarboxylic acid derivatives) as an oxidant in a solvent composed of only an inert solvent. The compound of the following general formula (II) selected as the substrate is reacted

[In the above formula (II),
The index m represents an integer of 1 to 10,
Each R ³ group represents a hydrogen atom and a group selected from the group consisting of optionally substituted linear, branched or cyclic C ₁ -C ₂₀ saturated or unsaturated hydrocarbon groups; wherein at least two R ³ groups are joined together optionally may be substituted, to form monocyclic, a C ₅ -C ₂₀ saturated or unsaturated ring in the form of bicyclo or tricyclo derivative,
Each X group represents an R ³ C═CR ³ or C (R ³ ) ₂ group;
Possible rings formed by said R ³ group or said at least two R ³ groups can optionally have up to 5 functional groups selected from the group consisting of carbonyl, carboxyl and ether]
As the corresponding lactone, a compound represented by the following formula (II ′) is obtained,

The water content of the reaction medium is less than 15% w / w,
Said catalyst system comprises the following A) formulas R ⁷ COOM, (R ⁷ COO) ₂ M ′, M ₂ CO ₃ , MHCO ₃ , M′CO ₃ , MOOH, M ₂ O ₂ , M′O ₂ , MOR ⁷ , And M ′ (OR ⁷ ) ₂ , M represents an alkali metal, M ′ represents an alkaline earth metal, and R ⁷ represents a hydrogen atom or a linear, branched or cyclic C ₁ -C ₁₅ alkyl. Or represents an aromatic group which may be halogenated;
B) a polycarboxylate M or M ', polycarboxylates carboxyl group portion is completely deprotonated;
_C) C 5 ~C ₂₀ β- dialdimine, beta-diketimine, beta-diketone or beta-ketoester and _C 5 _{-C 20} crown ether, cryptand, alkali having a ligand selected from the group consisting of po da command or Schiff base metal or alkaline earth metal salt or complex; and D) a), B) and C) Ri Do because only a compound selected from the group consisting of the compounds described in, also,
The inert solvent is a solvent that is not oxidized by H ₂ O ₂ and does not react with the compound of formula (II) under reaction conditions.
A process for producing a lactone, characterized in that In the formula (II),
The index m represents an integer of 1 to 4,
R ³ groups each represent a hydrogen atom and a group selected from the group consisting of optionally substituted linear, branched or cyclic C ₁ -C ₁₀ saturated or unsaturated hydrocarbon groups, At least two of the R ³ groups are optionally joined together to form an optionally substituted C ₅ -C ₁₄ saturated or unsaturated ring in the form of a monocyclo, bicyclo or tricyclo derivative;
Each X group represents an R ³ C═CR ³ or C (R ³ ) ₂ group;
The possible ring formed by said R ³ group or said at least two R ³ groups can optionally have up to 5 functional groups selected from the group consisting of carbonyl, carboxyl and ether. Lactone production method. Cyclopentanone or cyclohexanone optionally substituted by one or two linear or branched C ₁ -C ₉ alkyl or alkenyl groups, C ₁₁ -C ₁₆ bicyclo of octahydronaphthalene or tricyclo derivatives and C ₆ -C ₁₆ monocyclic, is selected from the group consisting of bicyclo or tricycloalkyl alkene derivatives, lactone process of claim 13 wherein. Before Ki溶 agent, aromatic compounds, ethers, esters, acyclic ketones, alcohols, glycols, amides, phosphates, halogenated hydrocarbons, and is selected from the group consisting of mixtures thereof, lactones produced according to claim 13, wherein Method. Before Ki溶 agent, chlorobenzene, t-amyl alcohol, t- butyl methyl ether, t-amyl methyl ether, dioxane, ethyl acetate, ethyl propionate, n- propyl acetate, n- propyl formate, butyl formate, The process for producing a lactone according to claim 16, selected from the group consisting of isopropyl acetate, butyl acetate and isobutyl acetate. The catalyst system is the following: E) Formula R ⁸ COOM, (R ⁸ COO) ₂ M ′, M ₂ CO ₃ , MHCO ₃ , M′CO ₃ , M ₂ O ₂ , M′O ₂ , MOR ⁸ , And M ′ (OR ⁸ ) ₂ , M represents Li, Na or K, M ′ represents Mg or Ca, R ⁸ represents a hydrogen atom or a linear, branched or cyclic C _{1 to} C _8. Represents an alkyl group;
F) an alkali metal salt or complex of formula ML, wherein L is a C _{5 to} C ₁₅ β-diketonate or deprotonated β-keto ester; and G) from a mixture of compounds described in E) and F) The method for producing a lactone according to claim 13, comprising only a compound selected from the group consisting of: ^{R 8 COO -, - OR 8} , β- diketonate and deprotonated beta-ketoester acetate, propionate, 2-ethylhexanoate, naphthenate, benzoate, 2,4-dichloro benzoate, propylate, ethylate, t-pentylate, _{[(CH 3) 3 CCOCHCOC (} CH 3) 3] -, [F 3 CCOCHCOCF 3] -, [C 6 H 5 COCHCOCH 3] -, [CH 3 COCHCOCH 3] - and _{[CH 3 COCHCOOCH 2 CH 2 OCH} 3 ] ^- it can be, lactone process according to claim 18, wherein.   The method for producing a lactone according to claim 13, wherein the catalyst system is a salt or complex of Li, Na or K. The catalyst system, carbonates, hydrogenoformans carbonate, acetate, propylate, or _C 5 _{-C 15} beta-diketonate salt or complex, according to claim 13 lactone method according.   The method for producing a lactone according to claim 13, wherein the water content of the reaction medium is less than 5% w / w.   The method for producing a lactone according to claim 13, wherein water is continuously removed from the reaction medium.